A variety of alkoxythiophenes have been synthesized that represent ideal subunits for the synthesisof a new class of thermotropic liquid crystals via palladium-catalyzed cross-coupling reactions andorganometallic derivatization. The methodology used represents the first highly efficient synthesisof alkoxythiophenes unlike previous pathways that have presented serious synthetic difficultieswhen the alkoxy chain consisted of more than four carbon atoms. The scope of the new procedure(relative to liquid crystalline intermediates) is presented and is compared and contrasted with thecurrent literature.